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The Darkinjung people (specifically the Wonarua tribe) originally inhabited the Pokolbin area for more than 3000 years. They were the major inhabitants at the time of European contact. This contact was disastrous for the Darkinjung people. Many were murdered or died as a result of European diseases. Others were forced onto neighbouring tribal territory and killed. Many lost the will to live and occupied shanty ghettos on the edge of white settlements. Settler pressure on land also constricted traditional tribal and clannish domains, often leading to tribal fighting.[11]

Viticulture in the Hunter Valley is often considered to have commenced with James Busby. In the 1820s he studied oenology, wrote a treatise and guidance manual on the subject and briefly taught viticulture at a Liverpool farm school. In 1831 he undertook a tour of French and Spanish vineyards which resulted in two published journals of the trip.[12] He returned with 570 cuttings of which 363 survived carefully wrapped in moss, sand and soil. [13]Half went to the newly established Royal Botanical Gardens in Sydney. The rest he took with him to the family estate of Kirkton, just north of Belford on the Hunter river run by his brother-in-law William Kelman. Also in 1828 George Wyndam planted vines at his Dalwood estate with the first shiraz being planted there in 1830.[14] The Drayton family established a vineyard at Pokolbin around the late 1850s and the Tyrrells Estate was set up in 1859 with Frederick Wilkinson planting vines at Oakdale in 1866. After the Robertson Land Act was introduced in 1861 the way was opened for small landholders and more people began to settle in the Rothbury/Pokolbin area.[15] The main farming activities were wheat, tobacco, dairy and grapes. By the 1930s the area was known for producing quality wines.

The area includes numerous wineries, ranging from large multi-national to small family run operations, which are a popular tourist destination. In addition to long-established names like Drayton, Lindeman, McWilliams Mount Pleasant, Tulloch, Lake's Folly and Tyrrell, newer plantings from the likes of Brokenwood Wines, Don Francois, Allandale, Petersons and Bimbadgen can be found. Much of the rolling countryside around Pokolbin is under vine with the traditional varieties Shiraz and Sémillon still dominating but extensive plantings of Chardonnay, Cabernet Sauvignon and the occasional plot of Pinot noir can be seen.[16]

Despite hot summers and freezing winters with frequent frost presenting a constant challenge to vineyard managers and winemakers, the area is a successful wine growing region thanks to mountains that encircle three sides of the valley, the cloud cover, and afternoon easterly sea breezes which, during summer, help to mitigate the blazing sunshine and keep humidity moderated on the valley floor. Soil types vary from rich red volcanic soil from the long-extinct volcano of Mount View and sandy loam which benefits most white varieties. The red volcanic soil is found mostly on the southern ridges. However, it can be found in patches on the valley floor.

Over the decades, the style of Hunter whites and reds has changed vastly, from robust, muscular reds exhibiting the famous Hunter Valley "sweaty saddle" and extraordinarily long-lived Semillon whites to reds showing more fruit, complexity and delicacy and whites exhibiting fruit-driven characters.

Tourist accommodation in the area is plentiful due to the wine industry and Pokolbin's proximity to Sydney, which is 163 km (101 mi) to the south, reached via the Pacific Motorway. Accommodation includes country resorts, golfing resorts, motels and guest houses and hostels. There are many local restaurants where visitors can try local wines.

Attractions in the Pokolbin area include numerous wineries and Pokolbin village. The Hunter Valley Gardens span over 25 hectares (62 acres) of land in the heart of the Hunter vineyards at the foot of the Brokenback Range, west of Cessnock.[17] Potters Brewery, established in 2002, is the Hunter's first microbrewery located in the heritage listed "Brick Beehive Kilns of Nulkaba".[18] The Great North Walk, a long-distance walking trail between Sydney and Newcastle, has an extension that goes to Pokolbin.